High charge density metallophosphate molecular sieves

ABSTRACT

A family of highly charged crystalline microporous metallophosphate molecular sieves designated PST-16 has been synthesized. These metallophosphates are represented by the empirical formula of: 
       R p+   r A m   + M x E y PO z    
     where A is an alkali metal such as potassium, R is an organoammonium cation such as ethyltrimethylammonium, M is a divalent metal such as zinc and E is a trivalent framework element such as aluminum or gallium. The PST-16 family of molecular sieves are stabilized by combinations of alkali and organoammonium cations, enabling unique metalloalumino(gallo)phosphate compositions and exhibit the CGS topology. The PST-17 family of molecular sieves has catalytic properties for carrying out various hydrocarbon conversion processes and separation properties for separating at least one component.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from Provisional Application No.62/341,174 filed May 25, 2016, the contents of which cited applicationare hereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

This invention relates to a family of charged metallophosphate-basedmolecular sieves designated PST-16. They are represented by theempirical formula of:

Rp+rA+mM2+xEyPOz

where A is an alkali metal such as potassium, R is at least onequaternary ammonium cation such as ethyltrimethylammonium, M is adivalent metal such as zinc and E is a trivalent framework element suchas aluminum or gallium. The PST-16 family of materials has the CGStopology.

BACKGROUND OF THE INVENTION

Zeolites are crystalline aluminosilicate compositions which aremicroporous and which are formed from corner sharing [AlO_(4/2)]⁻ andSiO_(4/2) tetrahedra. Numerous zeolites, both naturally occurring andsynthetically prepared are used in various industrial processes.Synthetic zeolites are prepared via hydrothermal synthesis employingsuitable sources of Si, Al and structure directing agents (SDAs) such asalkali metals, alkaline earth metals, amines, or organoammonium cations.The structure directing agents reside in the pores of the zeolite andare largely responsible for the particular structure that is ultimatelyformed. These species balance the framework charge associated withaluminum and can also serve as space fillers. Zeolites are characterizedby having pore openings of uniform dimensions, having a significant ionexchange capacity, and being capable of reversibly desorbing an adsorbedphase which is dispersed throughout the internal voids of the crystalwithout significantly displacing any atoms which make up the permanentzeolite crystal structure. Zeolites can be used as catalysts forhydrocarbon conversion reactions, which can take place on outsidesurfaces of the zeolite as well as on internal surfaces within the poresof the zeolite.

In 1982, Wilson et al. developed aluminophosphate molecular sieves, theso-called AlPOs, which are microporous materials that have many of thesame properties of zeolites, but are silica free, composed of[AlO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedra (See U.S. Pat. No. 4,319,440).Subsequently, charge was introduced to the neutral aluminophosphateframeworks via the substitution of SiO_(4/2) tetrahedra for [PO_(4/2)]⁺tetrahedra to produce the SAPO molecular sieves (See U.S. Pat. No.4,440,871). Another way to introduce framework charge to neutralaluminophosphates is to substitute [M²⁺O_(4/2)]²⁻ tetrahedra for[AlO_(4/2)]⁻ tetrahedra, which yield the MeAPO molecular sieves (seeU.S. Pat. No. 4,567,029). It is furthermore possible to introduceframework charge on AlPO-based molecular sieves via the introductionboth of SiO_(4/2) and [M²⁺O_(4/2)]²⁻ tetrahedra to the framework, givingMeAPSO molecular sieves (See U.S. Pat. No. 4,973,785).

In the early 1990's, high charge density molecular sieves, similar tothe MeAPOs but without the Al, were developed by Bedard (See U.S. Pat.No. 5,126,120) and Gier (See U.S. Pat. No. 5,152,972). These metalphosphates (sometimes arsenates, vanadates) were based on M²⁺ (M=Zn,Co), the general formula of which, in terms of the T-atoms, T²⁺-T⁵⁺, wasapproximately A⁺T²⁺T⁵⁺O₄, having framework charge densities similar toSi/Al=1 zeolites and were charge balanced by alkali cations, A⁺, in thepores. Later attempts to prepare metallophosphates of similarcompositions but with organic SDAs led to porous, but interruptedstructures, i.e., the structures contained terminal P—O—H and Zn—N bonds(See J. Mater. Chem., 1992, 2(11), 1127-1134.) Attempts at Alsubstitution in a zincophosphate network was carried out in the presenceof both alkali and organoammonium agents, specifically the most highlycharged organoammonium species, tetramethylammonium, but because of thehigh framework charge density, only the alkali made it into the pores tobalance framework charge (See U.S. Pat. No. 5,302,362). Similarly, in ahigh charge density zincophosphate system that yielded the zincphosphate analog of zeolite X, the synthesis in the presence of Na⁺ andTMA⁺ yielded a product that contained considerably less TMA⁺ than Na⁺(See Chem. Mater., 1991, 3, 27-29).

To bridge the rather large charge density gap between the MeAPOs of U.S.Pat. No. 4,567,029 and the aforementioned alkali-stabilizedMe²⁺-phosphates of Bedard and Gier, Stucky's group developed a synthesisroute using amines, often diamines in ethylene glycol solvent. They wereable to make high charge density, small pore MeAPOs in which theconcentrations of Co²⁺ and Al³⁺ in R(Co_(x)Al_(1-x))PO₄ were varied suchthat 0.33≦x≦0.9 in the so-called ACP series of materials, the aluminumcobalt phosphates (See Nature, 1997, 388, 735). Continuing with thissynthesis methodology utilizing ethylene glycol solution matching theamines to framework charge densities for R(M²⁺ _(x)Al_(1-x))PO₄, suchthat 0.4≦x≦0.5, (M²⁺=Mg²⁺, Mn²⁺, Zn²⁺, Co²⁺) the large pore materialsUCSB-6, -8 and -10 were isolated (See Science, 1997, 278, 2080). Crystaldimensions isolated from that work were often on the order of hundredsof microns. Similarly, this approach also yielded MeAPO analogs ofzeolite rho of the composition RM²⁺ _(0.5)Al_(0.5)PO₄, where R═N,N′-diisopropyl-1, 3-propanediamine, M²⁺=Mg²⁺, Co²⁺ and Mn²⁺. Cowleyfollowed this ethylene glycol-based strategy to prepare the cobalt andzinc gallium phosphates using quinuclidine as the SDA, that have the CGStopology and a framework charge density of −0.125/T-atom (SeeMicroporous and Mesoporous Materials 28, 1999 163-172). Similarly, Linand Wang used 1,2 diaminocyclohexane (DACH) with the ethylene glycolapproach to prepare a Zn—Ga phosphate of CGS topology with higher Znincorporation than the Cowley work, realizing a framework charge densityof −0.25/T-atom for (H₂DACH)Zn₂Ga₂(PO₄)₄ (See Chemistry of Materials,12, 2000 3617-3623). The reliance of these synthesis approaches on anethylene glycol solvent does not lend itself well to industrial scale,from both a safety and environmental point of view. Other than thiswork, there has been little activity in this intermediate charge densityregion, where 0.2≦x≦0.9 for the [M²⁺ _(x)(Al,Ga)_(1-x)PO₄]^(x−)compositions.

Pursuing aqueous chemistry, Wright et al. used highly chargedtriquaternary ammonium SDAs to make new MeAPO materials (See Chem.Mater., 1999, 11, 2456-2462). One of these materials, STA-5 with the BPHtopology, (Mg_(2.1)Al_(11.9)P₁₄O₂₈), exhibited significant substitutionof Mg²⁺ for Al³+, up to about 15%, but less substitution than seen inStucky's non-aqueous ethylene glycol approach.

More recently, Lewis et al. developed aqueous solution chemistry usingquaternary ammonium cations leading to high charge density SAPO, MeAPO,and MeAPSO materials, enabling greater substitution of SiO_(4/2) and[M²⁺O_(4/2)]²⁻ into the framework for [PO_(4/2)]⁺ and [AlO_(4/2)]⁻,respectively, using the ethyltrimethylammonium (ETMA⁺) anddiethyldimethylammonium (DEDMA⁺) SDAs. These materials include ZnAPO-57(U.S. Pat. No. 8,871,178), ZnAPO-59 (U.S. Pat. No. 8,871,177), ZnAPO-67(U.S. Pat. No. 8,697,927), and MeAPSO-64 (U.S. Pat. No. 8,696,886). Therelationship between the increasing product charge densities andreaction parameters, namely the ETMAOH(DEDMAOH)/H₃PO₄ ratios, wereoutlined in the literature (See Microporous and Mesoporous Materials,189, 2014, 49-63). The incorporation of M²⁺ observed in these systemswas such that for the formulation [M²⁺ _(x)Al_(1-x)PO₄]^(x−), x˜0.3,about 30% substitution of Al and a framework charge density of−0.15/T-atom.

Applicants have now synthesized a new family of highly chargedmetallophosphate framework materials, designated PST-16, with highercharge densities than the MeAPOs of U.S. Pat. No. 4,567,029 and theZnAPO materials isolated by Lewis. Contrary to the work cited above inwhich high framework charge density metallophosphates are prepared fromamines in ethylene glycol solution, the current materials are preparedfrom aqueous solution utilizing a combination quaternary ammonium andalkali cations. The PST-16 materials have the CGS topology (See Databaseof Zeolite Structures, www.iza-structure.org/databases) and exhibit arange of framework charge densities that are greater than those observedby Cowley and comparable to or higher than those observed by Lin andWang. The utility of alkali in metalloaluminophosphate-based systems isuncommon and in combination with quaternary ammonium cations under theright conditions enables this system to achieve the charge densities anddesired midrange compositions between the low charge density MeAPOs ofU.S. Pat. No. 4,567,029 and high charge density M²⁺-phosphate extremes.

SUMMARY OF THE INVENTION

As stated, the present invention relates to a new family ofmetallophosphate molecular sieves designated PST-16. Accordingly, oneembodiment of the invention is a microporous crystalline material havinga three-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and[PO_(4/2)]⁺ tetrahedral units and an empirical composition in the assynthesized form and on an anhydrous basis expressed by an empiricalformula of:

Rp+rA+mM2+xEyPOz

where R is at least one quaternary ammonium cation selected from thegroup consisting of ethyltrimethylammonium (ETMA⁺),diethyldimethylammonium (DEDMA⁺), hexamethonium (HM²⁺), choline[Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium, trimethylbutylammonium,trimethylisopropylammonium, tetramethylammonium (TMA⁺),tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) and mixturesthereof, “r” is the mole ratio of R to P and has a value of about 0.1 toabout 1.0, “p” is the weighted average valence of R and varies from 1 to2, A is an alkali metal such as Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixturesthereof, “m” is the mole ratio of A to P and varies from 0.1 to 1.0, Mis a divalent element selected from the group of Zn, Mg, Co, Mn andmixtures thereof, “x” is the mole ratio of M to P and varies from 0.2 toabout 0.9, E is a trivalent element selected from the group consistingof aluminum and gallium and mixtures thereof, “y” is the mole ratio of Eto P and varies from 0.1 to about 0.8 and “z” is the mole ratio of O toP and has a value determined by the equation:

z=(m+p·r+2·x+3·y+5)/2

and is characterized in that it has the x-ray diffraction pattern havingat least the d-spacings and intensities set forth in Table A:

TABLE A 2Θ d (Å) I/I₀ % 8.28-8.06 10.67-10.96 vs 10.83-10.64 8.16-8.31 w11.68-11.47 7.57-7.71 w-m 12.49-12.15 7.08-7.28 m-vs 13.13-12.896.74-6.86 w 13.36-13.11 6.62-6.75 w 16.53-16.22 5.36-5.46 m-s16.91-16.59 5.24-5.34 w-m 17.24-16.97 5.14-5.22 w 19.28-19.03 4.60-4.66m-vs 19.62-19.36 4.52-4.58 w-m 21.93-21.39 4.05-4.15 m 22.32-21.873.98-4.06 w-m 22.84-22.49 3.89-3.95 w 23.14-22.78 3.84-3.90 w-m23.39-23.11  3.80-3.845 w-m 23.84-23.45 3.73-3.79 w-m 24.23-23.773.67-3.74 m 24.92-24.61  3.57-3.615 m-s 26.35-26.11 3.38-3.41 w-m26.79-26.35 3.325-3.38  w-m 27.38-26.79 3.255-3.325 m-s 29.06-28.493.07-3.13 m-s 29.50-28.97 3.025-3.08  m 31.70-30.97  2.82-2.885 w-m32.00-31.36 2.795-2.85  m 33.34-32.72 2.685-2.735 w-m 34.33-34.02 2.61-2.633 w-m

Another embodiment of the invention is a process for preparing thecrystalline metallophosphate molecular sieve described above. Theprocess comprises forming a reaction mixture containing reactive sourcesof R, A, M, E and P and heating the reaction mixture at a temperature ofabout 60° C. to about 200° C. for a time sufficient to form themolecular sieve, the reaction mixture having a composition expressed interms of mole ratios of the oxides of:

aR2/pO:bA2O:cMO:E2O3:dP2O5:eH2O

where “a” has a value of about 2.1 to about 100, “b” has a value ofabout 0.1 to about 8.0, “c” has a value of about 0.25 to about 8, “d”has a value of about 1.69 to about 25, and “e” has a value from 30 to5000.

Yet another embodiment of the invention is a hydrocarbon conversionprocess using the above-described molecular sieve as a catalyst. Theprocess comprises contacting at least one hydrocarbon with the molecularsieve at conversion conditions to generate at least one convertedhydrocarbon.

Still another embodiment of the invention is a separation process usingthe crystalline PST-16 material. The process may involve separatingmixtures of molecular species or removing contaminants by contacting afluid with the PST-16 molecular sieve. Separation of molecular speciescan be based either on the molecular size (kinetic diameter) or on thedegree of polarity of the molecular species. Removing contaminants maybe by ion exchange with the molecular sieve.

DETAILED DESCRIPTION OF THE INVENTION

Applicants have prepared a family of high charge density crystallinemicroporous metallophosphate compositions with the CGS topology,designated PST-16. Compared to other early MeAPO materials, the PST-16family of materials contains much more M²⁺ and exhibits high framework(FW) charge densities that unlike the other MeAPOs use of alkali cationsin addition to organoammonium ions to balance the FW charge. The instantmicroporous crystalline material (PST-16) has an empirical compositionin the as-synthesized form and on an anhydrous basis expressed by theempirical formula:

Rp+rA+mM2+xEyPOz

where A is at least one alkali cation and is selected from the group ofalkali metals. Specific examples of the A cations include but are notlimited to lithium, sodium, potassium, rubidium, cesium and mixturesthereof. R is at least one quaternary ammonium cation, examples of whichinclude but are not limited to ethyltrimethylammonium (ETMA⁺),diethyldimethylammonium (DEDMA⁺), hexamethonium (HM²⁺), choline[Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium, trimethylbutylammonium,trimethylisopropylammonium, tetramethylammonium (TMA⁺),tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) and mixturesthereof, and “r” is the mole ratio of R to P and varies from about 0.1to about 1.0, while “p” is the weighted average valence of R and variesfrom about 1 to 2. M and E are tetrahedrally coordinated and in theframework, M is a divalent element selected from the group of Zn, Mg,Co, Mn and mixtures thereof, while E is a trivalent element selectedfrom aluminum and gallium and mixtures thereof. The value of “m” is themole ratio of A to P and varies from 0.1 to about 1.0, “x” is mole ratioof M to P and varies from 0.2 to about 0.9, while the ratio of E to P isrepresented by “y” which varies from about 0.10 to about 0.8. Lastly,“z” is the mole ratio of O to P and is given by the equation:

z=(m+r·p+3·x+3·y+5)/2.

When only one type of R quaternary ammonium cation is present, then theweighted average valence is just the valence of that cation, e.g., +1 or+2. When more than one R cation is present, the total amount of R isgiven by the equation:

R _(r) ^(p+) =R _(r1) ^((p1)+) +R _(r2) ^((p2)+) +R _(r3) ^((p3)+)+ . ..

the weighted average valence “p” is given by:

$p = \frac{{r\; {1 \cdot p}\; 1} + {r\; {2 \cdot p}\; 2} + {r\; {3 \cdot p}\; 3} + \ldots}{{r\; 1} + {r\; 2} + {r\; 3} + \ldots}$

It has also been noted that in the PST-16 materials of this inventionthat a portion of M²⁺ may also reside in the pores, likely in a chargebalancing role.

The microporous crystalline metallophosphate PST-16 is prepared by ahydrothermal crystallization of a reaction mixture prepared by combiningreactive sources of R, A, E, phosphorous and M. A preferred form of thePST-16 materials is when E is Al. The sources of aluminum include butare not limited to aluminum alkoxides, precipitated aluminas, aluminummetal, aluminum hydroxide, aluminum salts, alkali aluminates and aluminasols. Specific examples of aluminum alkoxides include, but are notlimited to aluminum ortho sec-butoxide and aluminum ortho isopropoxide.Sources of phosphorus include, but are not limited to, orthophosphoricacid, phosphorus pentoxide, and ammonium dihydrogen phosphate. Sourcesof M include but are not limited to zinc acetate, zinc chloride, cobaltacetate, cobalt chloride, magnesium acetate, magnesium nitrate,manganese sulfate, manganese acetate and manganese nitrate. Sources ofthe other E elements include but are not limited to precipitated galliumhydroxide, gallium chloride, gallium sulfate or gallium nitrate. Sourcesof the A metals include the halide salts, nitrate salts, hydroxidesalts, acetate salts, and sulfate salts of the respective alkali metals.R is at least one quaternary ammonium cation selected from the groupconsisting of ETMA⁺, DEDMA⁺, HM²⁺, choline, trimethylpropylammonium,trimethylisopropylammonium, trimethylbutylammonium, TMA⁺,tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) and mixturesthereof, and the sources include the hydroxide, chloride, bromide,iodide and fluoride compounds. Specific examples include withoutlimitation ethyltrimethylammonium hydroxide, ethyltrimethylammoniumchloride, diethyldimethylammonium chloride, diethyldimethylammoniumhydroxide, hexamethonium dihydroxide, hexamethonium dichloride, cholinehydroxide, choline chloride, trimethylisopropylammonium hydroxide,propyltrimethylammonium chloride and tetramethylammonium bromide. In oneembodiment R is ETMA⁺. In another embodiment, R isdiethyldimethylammonium. In yet another embodiment, R istetraethylammonium. Finally, R may also be a combination of ETMA⁺ and atleast one organoammonium cation selected from the group consisting ofcholine, DEDMA⁺, TMA⁺, HM²⁺, trimethylpropylammonium,trimethylisopropylammonium, trimethylbutylammonium, TEA⁺, and TPA⁺.

The reaction mixture containing reactive sources of the desiredcomponents can be described in terms of molar ratios of the oxides bythe formula:

aR_(2/p)O:bA₂O:cMO:E₂O₃ :dP₂O₅ :eH₂O

where “a” varies from about 2.1 to about 100, “b” varies from about 0.1to about 8, “c” varies from about 0.25 to about 8, “d” varies from about1.69 to about 25, and “e’ varies from 30 to 5000. If alkoxides are used,it is preferred to include a distillation or evaporative step to removethe alcohol hydrolysis products. The reaction mixture is now reacted ata temperature of about 60° C. to about 200° C. and preferably from about95° C. to about 175° C. for a period of about 1 day to about 3 weeks andmore preferably for a time of about 1 day to about 7 days in a sealedreaction vessel at autogenous pressure. After crystallization iscomplete, the solid product is isolated from the heterogeneous mixtureby means such as filtration or centrifugation, and then washed withdeionized water and dried in air at ambient temperature up to about 100°C. PST-16 seeds can optionally be added to the reaction mixture in orderto accelerate or otherwise enhance the formation of the desiredmicroporous composition.

The PST-16 metallophosphate-based material, which is obtained from theabove-described process, is characterized by the x-ray diffractionpattern, having at least the d-spacings and relative intensities setforth in Table A below.

TABLE A 2Θ d (Å) I/I₀ % 8.28-8.06 10.67-10.96 vs 10.83-10.64 8.16-8.31 w11.68-11.47 7.57-7.71 w-m 12.49-12.15 7.08-7.28 m-vs 13.13-12.896.74-6.86 w 13.36-13.11 6.62-6.75 w 16.53-16.22 5.36-5.46 m-s16.91-16.59 5.24-5.34 w-m 17.24-16.97 5.14-5.22 w 19.28-19.03 4.60-4.66m-vs 19.62-19.36 4.52-4.58 w-m 21.93-21.39 4.05-4.15 m 22.32-21.873.98-4.06 w-m 22.84-22.49 3.89-3.95 w 23.14-22.78 3.84-3.90 w-m23.39-23.11  3.80-3.845 w-m 23.84-23.45 3.73-3.79 w-m 24.23-23.773.67-3.74 m 24.92-24.61  3.57-3.615 m-s 26.35-26.11 3.38-3.41 w-m26.79-26.35 3.325-3.38  w-m 27.38-26.79 3.255-3.325 m-s 29.06-28.493.07-3.13 m-s 29.50-28.97 3.025-3.08  m 31.70-30.97  2.82-2.885 w-m32.00-31.36 2.795-2.85  m 33.34-32.72 2.685-2.735 w-m 34.33-34.02 2.61-2.633 w-m

The PST-16 may be modified in many ways to tailor it for use in aparticular application. Modifications include calcination, ammoniacalcinations, ion-exchange, steaming, various acid extractions, ammoniumhexafluorosilicate treatment, or any combination thereof, as outlinedfor the case of UZM-4 in U.S. Pat. No. 6,776,975 B1 which isincorporated by reference in its entirety. In addition, properties thatmay be modified include porosity, adsorption, framework composition,acidity, thermal stability, ion-exchange capacity, etc.

As synthesized, the PST-16 material will contain some of theexchangeable or charge balancing cations in its pores. Theseexchangeable cations can be exchanged for other cations, or in the caseof organic cations, they can be removed by heating under controlledconditions. A preferred method of removing organic cations from thepores is ammonia calcination. Calcination in air converts the organiccations in the pores to protons, which can lead to the loss of somemetal, for example Al, from the framework upon exposure to ambientatmospheric water vapor. When the calcination is carried out in anammonia atmosphere, the organic cation in the pore is replaced by NH₄ ⁺cation and the framework remains intact (See STUDIES IN SURFACE SCIENCE,(2004) vol. 154, p. 1324-1331). Typical conditions for ammoniacalcinations include the use of gaseous anhydrous ammonia flowing at arate of 1.1 l/min while ramping the sample temperature at 5° C./min to500° C. and holding at that temperature for a time ranging from 5minutes to an hour. The resulting ammonium/alkali form of PST-16 hasessentially the diffraction pattern of Table A. Once in this form, theammonia calcined material may be ion-exchanged with H⁺, NH₄ ⁺, alkalimetals, alkaline earth metals, transition metals, rare earth metals, orany mixture thereof, to achieve a wide variety of compositions with thePST-16 framework in superior condition.

When PST-16 or its modified forms are calcined in air, there can be aloss of metal from the framework, such as Al, which can alter the x-raydiffraction pattern from that observed for the as-synthesized PST-16(See STUDIES IN SURFACE SCIENCE, (2004) vol. 154, p. 1324-1331). Typicalconditions for the calcination of the PST-16 sample include ramping thetemperature from room temperature to a calcination temperature of 400°to 600° C., preferably a calcination temperature of 450° to 550° C. at aramp rate of 1 to 5° C./min, preferably a ramp rate of 2 to 4° C./min,the temperature ramp conducted in an atmosphere consisting either offlowing nitrogen or flowing clean dry air, preferably an atmosphere offlowing nitrogen. Once at the desired calcination temperature, if thecalcination atmosphere employed during the temperature ramp is flowingclean dry air, it may remain flowing clean dry air. If the calcinationatmosphere during the ramp was flowing nitrogen, it may remain flowingnitrogen at the calcination temperature or it may be immediatelyconverted to clean dry air; preferably at the calcination temperaturethe calcination atmosphere will remain flowing nitrogen for a period of1-10 hours and preferably for a period of 2-4 hours before convertingthe calcination atmosphere to flowing clean dry air. The final step ofthe calcination is a dwell at the calcination temperature in clean dryair. Whether the calcination atmosphere during the initial temperatureramp was flowing nitrogen or flowing clean dry air, once at thecalcination temperature and once the calcination atmosphere is clean dryair, the PST-16 sample will spend a period of 1-24 hours and preferablya period of 2-6 hours under these conditions to complete the calcinationprocess.

The crystalline PST-16 materials of this invention can be used forseparating mixtures of molecular species, removing contaminants throughion exchange and catalyzing various hydrocarbon conversion processes.Separation of molecular species can be based either on the molecularsize (kinetic diameter) or on the degree of polarity of the molecularspecies.

The PST-16 compositions of this invention can also be used as a catalystor catalyst support in various hydrocarbon conversion processes.Hydrocarbon conversion processes are well known in the art and includecracking, hydrocracking, alkylation of both aromatics and isoparaffin,isomerization, polymerization, reforming, hydrogenation,dehydrogenation, transalkylation, dealkylation, hydration, dehydration,hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanol toolefins, methanation and syngas shift process. Specific reactionconditions and the types of feeds which can be used in these processesare set forth in U.S. Pat. No. 4,310,440, U.S. Pat. No. 4,440,871 andU.S. Pat. No. 5,126,308, which are incorporated by reference. Preferredhydrocarbon conversion processes are those in which hydrogen is acomponent such as hydrotreating or hydrofining, hydrogenation,hydrocracking, hydrodenitrogenation, hydrodesulfurization, etc.

Hydrocracking conditions typically include a temperature in the range of400° to 1200° F. (204-649° C.), preferably between 600° and 950° F.(316-510° C.). Reaction pressures are in the range of atmospheric toabout 3,500 psig (24,132 kPa g), preferably between 200 and 3000 psig(1379-20,685 kPa g). Contact times usually correspond to liquid hourlyspace velocities (LHSV) in the range of about 0.1 hr⁻¹ to 15 hr⁻¹,preferably between about 0.2 and 3 hr⁻¹. Hydrogen circulation rates arein the range of 1,000 to 50,000 standard cubic feet (scf) per barrel ofcharge (178-8,888 std. m³/m³), preferably between 2,000 and 30,000 scfper barrel of charge (355-5,333 std. m³/m³). Suitable hydrotreatingconditions are generally within the broad ranges of hydrocrackingconditions set out above.

The reaction zone effluent is normally removed from the catalyst bed,subjected to partial condensation and vapor-liquid separation and thenfractionated to recover the various components thereof. The hydrogen,and if desired some or all of the unconverted heavier materials, arerecycled to the reactor. Alternatively, a two-stage flow may be employedwith the unconverted material being passed into a second reactor.Catalysts of the subject invention may be used in just one stage of sucha process or may be used in both reactor stages.

Catalytic cracking processes are preferably carried out with the PST-16composition using feedstocks such as gas oils, heavy naphthas,deasphalted crude oil residua, etc. with gasoline being the principaldesired product. Temperature conditions of 850° to 1100° F. (455° C. to593° C.), LHSV values of 0.5 hr⁻¹ to 10 hr⁻¹ and pressure conditions offrom about 0 to 50 psig (0-345 kPa) are suitable.

Alkylation of aromatics usually involves reacting an aromatic (C₂ toC₁₂), especially benzene, with a monoolefin to produce a linear alkylsubstituted aromatic. The process is carried out at an aromatic: olefin(e.g., benzene:olefin) ratio of between 5:1 and 30:1, a LHSV of about0.3 to about 6 hr⁻¹, a temperature of about 100° to about 250° C. andpressures of about 200 to about 1000 psig (1,379-6,895 kPa). Furtherdetails on apparatus may be found in U.S. Pat. No. 4,870,222 which isincorporated by reference.

Alkylation of isoparaffins with olefins to produce alkylates suitable asmotor fuel components is carried out at temperatures of −30° to 40° C.,pressures from about atmospheric to about 6,894 kPa (1,000 psig) and aweight hourly space velocity (WHSV) of 0.1 hr⁻¹ to about 120 hr⁻¹.Details on paraffin alkylation may be found in U.S. Pat. No. 5,157,196and U.S. Pat. No. 5,157,197, which are incorporated by reference.

The conversion of methanol to olefins is effected by contacting themethanol with the PST-16 catalyst at conversion conditions, therebyforming the desired olefins. The methanol can be in the liquid or vaporphase with the vapor phase being preferred. Contacting the methanol withthe PST-16 catalyst can be done in a continuous mode or a batch modewith a continuous mode being preferred. The amount of time that themethanol is in contact with the PST-16 catalyst must be sufficient toconvert the methanol to the desired light olefin products. When theprocess is carried out in a batch process, the contact time varies fromabout 0.001 hrs to about 1 hr and preferably from about 0.01 hr to about1.0 hr. The longer contact times are used at lower temperatures whileshorter times are used at higher temperatures. Further, when the processis carried out in a continuous mode, the Weight Hourly Space Velocity(WHSV) based on methanol can vary from about 1 hr⁻¹ to about 1000 hr⁻¹and preferably from about 1 hr⁻¹ to about 100 hr⁻¹.

Generally, the process must be carried out at elevated temperatures inorder to form light olefins at a fast enough rate. Thus, the processshould be carried out at a temperature of about 300° C. to about 600°C., preferably from about 400° C. to about 550° C. and most preferablyfrom about 450° C. to about 525° C. The process may be carried out overa wide range of pressure including autogenous pressure. Thus, thepressure can vary from about 0 kPa (0 psig) to about 1724 kPa (250 psig)and preferably from about 34 kPa (5 psig) to about 345 kPa (50 psig).

Optionally, the methanol feedstock may be diluted with an inert diluentin order to more efficiently convert the methanol to olefins. Examplesof the diluents which may be used are helium, argon, nitrogen, carbonmonoxide, carbon dioxide, hydrogen, steam, paraffinic hydrocarbons, e.g., methane, aromatic hydrocarbons, e. g., benzene, toluene and mixturesthereof. The amount of diluent used can vary considerably and is usuallyfrom about 5 to about 90 mole percent of the feedstock and preferablyfrom about 25 to about 75 mole percent.

The actual configuration of the reaction zone may be any well knowncatalyst reaction apparatus known in the art. Thus, a single reactionzone or a number of zones arranged in series or parallel may be used. Insuch reaction zones the methanol feedstock is flowed through a bedcontaining the PST-16 catalyst. When multiple reaction zones are used,one or more PST-16 catalysts may be used in series to produce thedesired product mixture. Instead of a fixed bed, a dynamic bed system,e. g., fluidized or moving, may be used. Such a dynamic system wouldfacilitate any regeneration of the PST-16 catalyst that may be required.If regeneration is required, the PST-16 catalyst can be continuouslyintroduced as a moving bed to a regeneration zone where it can beregenerated by means such as oxidation in an oxygen containingatmosphere to remove carbonaceous materials.

The following examples are presented in illustration of this inventionand are not intended as undue limitations on the generally broad scopeof the invention as set out in the appended claims. The products of thisinvention are designated with the general name PST-16, with theunderstanding that all of the PST-16 materials exhibit a structure withthe CGS topology.

The structure of the PST-16 compositions of this invention wasdetermined by x-ray analysis. The x-ray patterns presented in thefollowing examples were obtained using standard x-ray powder diffractiontechniques. The radiation source was a high-intensity, x-ray tubeoperated at 45 kV and 35 mA. The diffraction pattern from the copperK-alpha radiation was obtained by appropriate computer based techniques.Flat compressed powder samples were continuously scanned at 2° to 56°(2θ). Interplanar spacings (d) in Angstrom units were obtained from theposition of the diffraction peaks expressed as θ where θ is the Braggangle as observed from digitized data. Intensities were determined fromthe integrated area of diffraction peaks after subtracting background,“I_(o)” being the intensity of the strongest line or peak, and “I” beingthe intensity of each of the other peaks.

As will be understood by those skilled in the art the determination ofthe parameter 20 is subject to both human and mechanical error, which incombination can impose an uncertainty of about ±0.4° on each reportedvalue of 20. This uncertainty is, of course, also manifested in thereported values of the d-spacings, which are calculated from the 20values. This imprecision is general throughout the art and is notsufficient to preclude the differentiation of the present crystallinematerials from each other and from the compositions of the prior art. Insome of the x-ray patterns reported, the relative intensities of thed-spacings are indicated by the notations vs, s, m, and w whichrepresent very strong, strong, medium, and weak, respectively. In termsof 100×I/I_(o), the above designations are defined as:

w=0-15;m=15-60:s=60-80 and vs=80-100

In certain instances the purity of a synthesized product may be assessedwith reference to its x-ray powder diffraction pattern. Thus, forexample, if a sample is stated to be pure, it is intended only that thex-ray pattern of the sample is free of lines attributable to crystallineimpurities, not that there are no amorphous materials present.

In order to more fully illustrate the invention, the following examplesare set forth. It is to be understood that the examples are only by wayof illustration and are not intended as an undue limitation on the broadscope of the invention as set forth in the appended claims.

Example 1

A Teflon beaker was charged with 150 g ethyltrimethylammonium hydroxide(ETMAOH, 20%, SACHEM, Inc.) and placed under a high speed stirrer.Aluminum isopropoxide (Al(OiPr)₃, 13.3% Al, Sigma-Aldrich) waspre-ground in a mortar and 5.79 g was dissolved in the ETMAOH solutionwith stirring. This was followed by the dropwise addition of 19.57 gH₃PO₄ (85.7%, Sigma-Aldrich). The reaction mixture was allowed to stir.Separately, 6.26 g Zn(OAc)₂*2 H₂O was dissolved in 25.00 g de-ionizedwater. This solution was added dropwise to the reaction mixture. Then1.06 g KCl was dissolved in 35.00 g de-ionized water and added dropwiseto the reaction mixture with stirring. The reaction mixture wasdistributed among 7 Teflon-lined autoclaves and digested at 95, 125,150, and 175° C. at autogenous pressure for 44 and 165 hr. The solidproducts were isolated by centrifugation and washed with de-ionizedwater. The products from the 95, 125 and 150° C. digestions wereidentified as PST-16 with the CGS by powder x-ray diffraction. Table 1below shows the representative diffraction lines for the productdigested at 150° C. for 44 hr. Elemental analysis showed this productwas composed of the elemental ratios C/N=5.31, Al/P=0.51, Zn/P=0.53,K/P=0.25 and N/P=0.23, consistent with the stoichiometryETMA_(0.23)K_(0.25)Zn_(0.53)Al_(0.51)P.

TABLE 1 2-Θ d (Å) I/I₀ (%) 8.20 10.78 vs 10.72 8.24 w 11.56 7.65 w 12.387.14 m 13.02 6.80 w 13.25 6.68 w 16.42 5.39 s 16.81 5.27 w 17.17 5.16 w19.16 4.63 m 19.40 4.57 m 19.54 4.54 m 21.30 4.17 w 21.56 4.12 m 21.764.08 m 22.18 4.00 m 22.72 3.91 w 23.00 3.86 w 23.26 3.82 w 23.72 3.75 w24.10 3.69 m 24.798 3.59 m 26.26 3.39 w 26.68 3.34 w 27.22 3.27 m 27.923.19 m 28.92 3.08 m 29.34 3.04 m 30.34 2.94 w 30.66 2.91 w 31.48 2.84 m31.78 2.81 m 33.18 2.70 w 34.20 2.62 w

Example 2

A Teflon beaker was charged with 150.00 g ETMAOH (20%) and placed undera high speed stirrer. Aluminum isopropoxide (13.3% Al) was pre-ground ina mortar. The Al(OiPr)₃, 5.79 g, was then dissolved in the stirringETMAOH solution. This was followed by the dropwise addition of 19.57 gH₃PO₄ (85.7%), again with stirring. Separately, 6.26 g Zn(OAc)₂*2 H₂Owas dissolved in 30.03 g de-ionized water and added fast dropwise to thestirring reaction mixture. Then 2.82 g KOAc (99.4%) was dissolved in30.10 g de-ionized water and added dropwise to the reaction mixture. Thereaction mixture was distributed among 7 Teflon-lined autoclaves anddigested at autogenous pressures at temperatures of 95, 125, 150, and175° C., for either 46 or 165 hr or both. The solid products wereisolated by centrifugation and washed with de-ionized water. The samplefrom the 95° C./165 hr digestion was identified as PST-16 with the CGStopology by powder x-ray diffraction, the representative diffractionlines of which are shown in Table 2 below. Elemental analysis showedthis product was composed of the elemental ratios C/N=5.06, Al/P=0.43,Zn/P=0.60, K/P=0.41, and N/P=0.16, consistent with the stoichiometryETMA_(0.16)K_(0.41)Zn_(0.60)Al_(0.43)P.

TABLE 2 2-Θ d (Å) I/I₀ (%) 8.20 10.78 vs 10.74 8.23 w 11.54 7.66 m 12.387.14 s 13.02 6.80 w 13.22 6.69 w 16.44 5.39 m 16.78 5.28 w 17.16 5.16 w17.56 5.05 w 19.14 4.63 m 19.56 4.54 m 20.54 4.32 w 21.58 4.11 m 21.784.08 m 22.18 4.00 m 22.74 3.91 w 23.02 3.86 m 23.24 3.82 w 23.74 3.75 w24.10 3.69 m 24.82 3.58 m 26.24 3.39 m 26.66 3.34 w 27.24 3.27 s 27.823.20 m 28.94 3.08 s 29.34 3.04 m 30.36 2.94 m 30.70 2.91 w 31.52 2.84 m31.84 2.81 m 32.62 2.74 m 33.20 2.70 m 33.68 2.66 w 33.98 2.64 w 34.222.62 m 34.68 2.58 w 35.04 2.56 m

Example 3

A Teflon beaker was charged with 130.00 g ETMAOH (20%) and placed undera high speed stirrer. Aluminum isopropoxide (13.3% Al) was pre-ground ina mortar and 6.27 g was dissolved in the ETMAOH solution. Then 21.20 gH₃PO₄ (85.7%) was added dropwise while stirring continued. Separately,6.78 g Zn(OAc)₂*2 H₂O was dissolved in 30.39 g de-ionized water. Thissolution was added dropwise to the reaction mixture. Next, 1.53 g KOAc(99.4%) was dissolved in 25.00 g de-ionized water and the resultingsolution added dropwise to the reaction mixture. Vigorous stirring wasrequired to thin out the reaction mixture. The reaction mixture wasdistributed among 7 Teflon-lined autoclaves and digested at temperaturesof 95, 125, 150, and 175° C., for either 41 or 172 hr or both atautogenous pressures. The solid products were isolated by centrifugationand washed with de-ionized water. All seven of the products wereidentified as PST-16 with the CGS topology by powder x-ray diffraction.The representative diffraction lines for the 150° C. product digestedfor 172 hr are shown in Table 3 below. Elemental analysis showed thisproduct was composed of the elemental ratios C/N=5.06, Al/P=0.53,Zn/P=0.48, K/P=0.24, and N/P=0.24, consistent with the stoichiometryETMA_(0.24)K_(0.24)Zn_(0.48)Al_(0.53)P.

TABLE 3 2-Θ d (Å) I/I₀ (%) 8.20 10.78 vs 10.74 8.23 w 11.58 7.64 m 12.387.14 m 13.00 6.80 w 13.24 6.68 w 16.42 5.39 m 16.80 5.27 m 17.12 5.17 w19.16 4.63 vs 19.38 4.58 vs, sh 19.52 4.54 m 20.56 4.32 w 21.34 4.16 w21.78 4.08 m 22.16 4.01 m 22.74 3.91 w 23.00 3.86 m 23.26 3.82 m 23.723.75 m 24.08 3.69 m 24.80 3.59 m 26.26 3.39 m 26.66 3.34 m 27.18 3.28 m28.18 3.16 w 28.94 3.08 m 29.32 3.04 m 30.34 2.94 m 30.70 2.91 m 31.522.84 m 31.72 2.82 m 32.30 2.77 w 32.74 2.73 w 33.18 2.70 m 33.68 2.66 w34.22 2.62 m 34.68 2.58 w 35.02 2.56 m 35.58 2.52 w

Example 4

A Teflon beaker was charged with 145.00 g diethyldimethylammoniumhydroxide (DEDMAOH, 20% aqueous, SACHEM, Inc.) and placed under ahigh-speed stirring apparatus. Pre-ground aluminum isopropoxide (13.2%Al) was added and dissolved with stirring. This was followed by the fastdropwise addition of 16.69 g H₃PO₄ (85.7%). Separately, 5.34 gZn(OAc)₂*2H₂O was dissolved in 25.00 g de-ionized water. This solutionwas added to the reaction mixture dropwise and intermittently. Anadditional solution was prepared by dissolving 1.19 g KOAc (99.4%) in12.44 g de-ionized water, which was added dropwise to the reactionmixture. The mixture was allowed to stir and then was distributed among7 Teflon-lined autoclaves which were digested at temperatures of 95,125, 150, and 175° C., for either 48 or 181 hr or both at autogenouspressures. The solid products were isolated by centrifugation and washedwith de-ionized water. The products isolated from the 181 hr digestionsat 95° C. and 125° C. were identified as PST-16 with the CGS topology bypowder x-ray diffraction. The representative diffraction lines for theproduct from the 125° C./181 hr digestion are shown in Table 4 below.Elemental analysis showed this product was composed of the elementalratios C/N=5.42, Al/P=0.48, Zn/P=0.50, K/P=0.26, and N/P=0.25,consistent with the stoichiometryDEDMA_(0.25)K_(0.26)Zn_(0.50)Al_(0.48)P.

TABLE 4 2-Θ d (Å) I/I₀ (%) 8.14 10.86 vs 10.71 8.26 w 11.54 7.66 w 12.257.22 m 12.96 6.82 w 13.18 6.71 w 16.28 5.44 m 16.68 5.31 w 17.05 5.20 w19.10 4.64 m 19.42 4.57 w 21.26 4.18 w 21.52 4.13 m 21.98 4.04 w 22.583.93 w 22.88 3.88 m 23.22 3.83 w 23.53 3.78 w 23.88 3.72 m 24.12 3.69 w24.70 3.60 m 26.18 3.40 m 26.48 3.36 w 26.92 3.31 m 28.07 3.18 w 28.643.11 m 29.08 3.07 m 30.15 2.96 w 30.42 2.94 w 30.67 2.91 w 31.14 2.87 w31.52 2.84 m 32.56 2.75 w 32.86 2.72 w 33.72 2.66 w 34.12 2.63 m 34.782.58 w 35.02 2.56 w

Example 5

A Teflon beaker was charged with 116.00 g DEDMAOH (20%) and placed undera high-speed stirring apparatus. With stirring, the solution was dilutedwith 25.64 g de-ionized water. Pre-ground aluminum isopropoxide (13.2%Al), 4.97 g, was added and dissolved in the hydroxide solution. This wasfollowed by the dropwise addition of 16.69 g H₃PO₄ (85.7%). Separately,5.34 g Zn(OAc)₂*2H₂O was dissolved in 25.00 g de-ionized water. Thissolution was added dropwise to the stirring reaction mixture. Anothersolution was prepared by dissolving 1.19 g KOAc (99.4%) in 25.00 gde-ionized water. This was added dropwise to the reaction mixture whilecontinuing the stirring. The reaction mixture was homogenized furtherbefore it was distributed among 7 Teflon-lined autoclaves, which weredigested at temperatures of 95, 125, 150, and 175° C., for either 48 or170 hr or both at autogenous pressures. The solid products were isolatedby centrifugation and washed with de-ionized water. The productsisolated from all of the digestions were identified as PST-16 with theCGS topology by powder x-ray diffraction. The representative diffractionlines for the product from the 125° C./48 hr digestion are shown inTable 5 below. Elemental analysis showed this product was composed ofthe elemental ratios C/N=5.53, Al/P=0.49, Zn/P=0.50, K/P=0.25, andN/P=0.23, consistent with the stoichiometryDEDMA_(0.23)K_(0.25)Zn_(0.50)Al_(0.49)P.

TABLE 5 2-Θ d (Å) I/I₀ (%) 8.20 10.78 100 10.76 8.22 w 11.60 7.62 m12.33 7.17 m 13.04 6.79 w 13.28 6.66 w 16.38 5.41 m 16.74 5.29 w 17.105.18 w 19.20 4.62 m 19.50 4.55 m 20.58 4.31 w 21.34 4.16 w 21.64 4.10 m22.04 4.03 w 22.30 3.98 w 22.70 3.91 w 22.94 3.87 w 23.28 3.82 w 23.603.77 w 23.79 3.74 w 23.96 3.71 m 24.24 3.67 w 24.80 3.59 m 26.26 3.39 m26.56 3.35 w 27.00 3.30 m 28.12 3.17 w 28.72 3.11 m 29.14 3.06 m 30.242.95 w 30.54 2.93 w 30.71 2.91 w 31.22 2.86 w 31.56 2.83 m 32.96 2.72 w33.78 2.65 w 34.22 2.62 m 34.90 2.57 m 35.12 2.55 m 35.53 2.52 w

Example 6

A Teflon beaker was charged with 126.33 g ETMAOH (20 wt. %) and placedunder a high speed overhead stirrer. This was followed by the additionand dissolution of 6.26 g of Al(OiPr)₃ (98+%) with stirring. Then 20.79g of H₃PO₄ (85%) was added slowly while mixing continued. Separately,6.73 g of zinc acetate dihydrate was dissolved in 30 g of deionizedwater. The resulting Zn solution was then slowly added to theAl/P/ETMAOH solution while mixing with an overhead stirrer. In aseparate beaker, 1.80 g KBr was dissolved in 58.1 g deionized water.This was then added slowly to the reaction mixture while continuing tomix with an overhead stirrer, resulting in a clear solution. Thesolution was then divided between 4×125 ml Teflon-lined autoclaves anddigested for 4 days at 150° C. at autogenous pressure. The solidproducts were isolated by centrifugation and washed with de-ionizedwater. Analysis by powder x-ray diffraction showed that all of thereactions resulted in PST-16 products with the CGS topology.Representative diffraction lines for the product are shown in Table 6below.

TABLE 6 2Θ d (Å) I/I₀ % 8.23 10.74 vs 10.76 8.22 w 11.61 7.61 w 12.537.06 vs 13.07 6.77 w 13.29 6.66 w 16.47 5.38 m 16.85 5.26 w 17.19 5.15 w17.48 5.07 w 19.20 4.62 w 19.46 4.56 w 19.58 4.53 w 21.40 4.15 m 21.474.13 m 21.59 4.11 m 21.83 4.07 w 22.23 4.00 w 22.76 3.90 w 23.05 3.86 w23.31 3.81 w 23.77 3.74 w 24.15 3.68 w 24.83 3.58 w 26.29 3.39 w 26.703.34 w 27.26 3.27 m 27.92 3.19 m 28.22 3.16 m 28.98 3.08 m 29.39 3.04 w30.39 2.94 w 30.71 2.91 w 31.59 2.83 w 31.83 2.81 w 32.35 2.76 w 32.632.74 w 32.79 2.73 w 33.25 2.69 m 33.41 2.68 m 33.71 2.66 w 34.03 2.63 w34.27 2.61 w 34.63 2.59 w

1. A microporous crystalline metallophosphate material having athree-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and[PO_(4/2)]⁺ tetrahedral units and an empirical composition in the assynthesized form and on an anhydrous basis expressed by an empiricalformula of:Rp+rA+mM2+xEyPOz where R is at least one quaternary ammonium cationselected from the group consisting of ethyltrimethylammonium (ETMA⁺),diethyldimethylammonium (DEDMA⁺), hexamethonium (HM²⁺⁾, choline[Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium, trimethylbutylammonium,trimethylisopropylammonium, tetramethylammonium (TMA⁺),tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) and mixturesthereof, “r” is the mole ratio of R to P and has a value of about 0.1 toabout 1.0, “p” is the weighted average valence of R and varies from 1 to2, A is an alkali metal selected from the group consisting of Li⁺, Na⁺,K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is the mole ratio of A to Pand varies from 0.1 to 1.0, M is a divalent element selected from thegroup of Zn, Mg, Co, Mn and mixtures thereof, “x” is the mole ratio of Mto P and varies from 0.2 to about 0.9, E is a trivalent element selectedfrom the group consisting of aluminum and gallium and mixtures thereof,“y” is the mole ratio of E to P and varies from 0.1 to about 0.8 and “z”is the mole ratio of O to P and has a value determined by the equation:z=(m+p·r+2·x+3·y+5)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table A: TABLE A 2Θ d (Å) I/I₀ % 8.28-8.06 10.67-10.96 vs10.83-10.64 8.16-8.31 w 11.68-11.47 7.57-7.71 w-m 12.49-12.15 7.08-7.28m-vs 13.13-12.89 6.74-6.86 w 13.36-13.11 6.62-6.75 w 16.53-16.225.36-5.46 m-s 16.91-16.59 5.24-5.34 w-m 17.24-16.97 5.14-5.22 w19.28-19.03 4.60-4.66 m-vs 19.62-19.36 4.52-4.58 w-m 21.93-21.394.05-4.15 m 22.32-21.87 3.98-4.06 w-m 22.84-22.49 3.89-3.95 w23.14-22.78 3.84-3.90 w-m 23.39-23.11  3.80-3.845 w-m 23.84-23.453.73-3.79 w-m 24.23-23.77 3.67-3.74 m 24.92-24.61  3.57-3.615 m-s26.35-26.11 3.38-3.41 w-m 26.79-26.35 3.325-3.38  w-m 27.38-26.793.255-3.325 m-s 29.06-28.49 3.07-3.13 m-s 29.50-28.97 3.025-3.08  m31.70-30.97  2.82-2.885 w-m 32.00-31.36 2.795-2.85  m 33.34-32.722.685-2.735 w-m 34.33-34.02 2.61-2.633 w-m


2. The metallophosphate material of claim 1 where A is potassium.
 3. Themetallophosphate material of claim 1 where E is aluminum.
 4. Themetallophosphate material of claim 1 where R is ethyltrimethylammoniumcation, ETMA⁺.
 5. The metallophosphate material of claim 1 where R isthe diethyldimethylammonium cation, DEDMA⁺.
 6. The metallophosphatematerial of claim 1 where R is tetraethylammonium cation, TEA⁺.
 7. Acrystalline modified form of the crystalline microporousmetallophosphate of claim 1, comprising a three-dimensional framework of[M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedral units andderived by modifying the crystalline microporous metallophosphate ofclaim 1, the modifications including calcination, ammonia calcinations,ion-exchange, steaming, various acid extractions, ammoniumhexafluorosilicate treatment, or any combination thereof.
 8. A processfor preparing a microporous crystalline metallophosphate material havinga three-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and[PO_(4/2)]⁺ tetrahedral units and an empirical composition in the assynthesized form and on an anhydrous basis expressed by an empiricalformula of:R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z) where R is at least one quaternaryammonium cation selected from the group consisting ofethyltrimethylammonium (ETMA⁺), diethyldimethylammonium (DEDMA⁺),hexamethonium (HM²⁺), choline [Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium,trimethylbutylammonium, trimethylisopropylammonium, tetramethylammonium(TMA⁺), tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) andmixtures thereof, “r” is the mole ratio of R to P and has a value ofabout 0.1 to about 1.0, “p” is the weighted average valence of R andvaries from 1 to 2, A is an alkali metal selected from the groupconsisting of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is themole ratio of A to P and varies from 0.1 to 1.0, M is a divalent elementselected from the group of Zn, Mg, Co, Mn and mixtures thereof, “x” isthe mole ratio of M to P and varies from 0.2 to about 0.9, E is atrivalent element selected from the group consisting of aluminum andgallium and mixtures thereof, “y” is the mole ratio of E to P and variesfrom 0.1 to about 0.8 and “z” is the mole ratio of O to P and has avalue determined by the equation:z=(m+p·r+2·x+3·y+5)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table A: TABLE A 2Θ d (Å) I/I₀ % 8.28-8.06 10.67-10.96 vs10.83-10.64 8.16-8.31 w 11.68-11.47 7.57-7.71 w-m 12.49-12.15 7.08-7.28m-vs 13.13-12.89 6.74-6.86 w 13.36-13.11 6.62-6.75 w 16.53-16.225.36-5.46 m-s 16.91-16.59 5.24-5.34 w-m 17.24-16.97 5.14-5.22 w19.28-19.03 4.60-4.66 m-vs 19.62-19.36 4.52-4.58 w-m 21.93-21.394.05-4.15 m 22.32-21.87 3.98-4.06 w-m 22.84-22.49 3.89-3.95 w23.14-22.78 3.84-3.90 w-m 23.39-23.11  3.80-3.845 w-m 23.84-23.453.73-3.79 w-m 24.23-23.77 3.67-3.74 m 24.92-24.61  3.57-3.615 m-s26.35-26.11 3.38-3.41 w-m 26.79-26.35 3.325-3.38  w-m 27.38-26.793.255-3.325 m-s 29.06-28.49 3.07-3.13 m-s 29.50-28.97 3.025-3.08  m31.70-30.97  2.82-2.885 w-m 32.00-31.36 2.795-2.85  m 33.34-32.722.685-2.735 w-m 34.33-34.02  2.61-2.633 w-m

the process comprising forming a reaction mixture containing reactivesources of R, A, E, M and P, and heating the reaction mixture at atemperature of about 60° C. to about 200° C. for a time sufficient toform the metallophosphate molecular sieve, the reaction mixture having acomposition expressed in terms of mole ratios of the oxides of:aR_(2/p)O:bA₂O:cMO:E₂O₃ :dP₂O₅ :eH₂O where “a” has a value of about 2.1to about 100, “b” has a value of about 0.1 to about 8.0, “c” has a valueof about 0.25 to about 8, “d” has a value of about 1.69 to about 25, and“e” has a value from 30 to
 5000. 9. The process of claim 8 where theinitial reaction mixture is a clear solution before digestion.
 10. Theprocess of claim 8 where A is selected from the group consisting of Li⁺,Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof and the source of A isselected from the group consisting of halide salts, nitrate salts,acetate salts, sulfate salts, hydroxide salts and mixtures thereof. 11.The process of claim 8 where M is selected from the group consisting ofZn²⁺, Mn²⁺, Co²⁺ and Mg²⁺ and mixtures thereof and where the source of Mis selected from the group consisting of halide salts, nitrate salts,acetate salts, sulfate salts and mixtures thereof.
 12. The process ofclaim 8 where the source of E is selected from the group consisting ofaluminum isopropoxide, aluminum sec-butoxide, precipitated alumina,Al(OH)₃, alkali aluminate salts, aluminum metal, aluminum halide salts,aluminum sulfate salts, aluminum nitrate salts, precipitated galliumoxyhydroxide, gallium nitrate, gallium sulfate and mixtures thereof. 13.The process of claim 8 where the reaction mixture is reacted at atemperature of about 95° C. to about 175° C. for a time of about 1 dayto about 10 days.
 14. The process of claim 8 where R isethyltrimethylammonium, ETMA⁺.
 15. The process of claim 8 where R isdiethyldimethylammonium, DEDMA⁺.
 16. The process of claim 8 furthercomprising adding PST-16 seeds to the reaction mixture.
 17. Ahydrocarbon conversion process comprising contacting a hydrocarbonstream with a catalyst at hydrocarbon conversion conditions to generateat least one converted product, wherein the catalyst is selected fromthe group consisting of a crystalline microporous PST-16 material, amodified crystalline microporous PST-16 material and mixtures thereof,where PST-16 is a crystalline microporous metallophosphate having athree-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and[PO_(4/2)]⁺ tetrahedral units and an empirical composition in the assynthesized form and on an anhydrous basis expressed by an empiricalformula of:R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z) where R is at least one quaternaryammonium cation selected from the group consisting ofethyltrimethylammonium (ETMA⁺), diethyldimethylammonium (DEDMA⁺),hexamethonium (HM²⁺), choline [Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium,trimethylbutylammonium, trimethylisopropylammonium, tetramethylammonium(TMA⁺), tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) andmixtures thereof, “r” is the mole ratio of R to P and has a value ofabout 0.1 to about 1.0, “p” is the weighted average valence of R andvaries from 1 to 2, A is an alkali metal such as Li⁺, Na⁺, K⁺, Rb⁺ andCs⁺ and mixtures thereof, “m” is the mole ratio of A to P and variesfrom 0.1 to 1.0, M is a divalent element selected from the group of Zn,Mg, Co, Mn and mixtures thereof, “x” is the mole ratio of M to P andvaries from 0.2 to about 0.9, E is a trivalent element selected from thegroup consisting of aluminum and gallium and mixtures thereof, “y” isthe mole ratio of E to P and varies from 0.1 to about 0.8 and “z” is themole ratio of O to P and has a value determined by the equation:z=(m+p·r+2·x+3·y+5)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacings and intensities setforth in Table A: TABLE A 2Θ d (Å) I/I₀ % 8.28-8.06 10.67-10.96 vs10.83-10.64 8.16-8.31 w 11.68-11.47 7.57-7.71 w-m 12.49-12.15 7.08-7.28m-vs 13.13-12.89 6.74-6.86 w 13.36-13.11 6.62-6.75 w 16.53-16.225.36-5.46 m-s 16.91-16.59 5.24-5.34 w-m 17.24-16.97 5.14-5.22 w19.28-19.03 4.60-4.66 m-vs 19.62-19.36 4.52-4.58 w-m 21.93-21.394.05-4.15 m 22.32-21.87 3.98-4.06 w-m 22.84-22.49 3.89-3.95 w23.14-22.78 3.84-3.90 w-m 23.39-23.11  3.80-3.845 w-m 23.84-23.453.73-3.79 w-m 24.23-23.77 3.67-3.74 m 24.92-24.61  3.57-3.615 m-s26.35-26.11 3.38-3.41 w-m 26.79-26.35 3.325-3.38  w-m 27.38-26.793.255-3.325 m-s 29.06-28.49 3.07-3.13 m-s 29.50-28.97 3.025-3.08  m31.70-30.97  2.82-2.885 w-m 32.00-31.36 2.795-2.85  m 33.34-32.722.685-2.735 w-m 34.33-34.02  2.61-2.633 w-m

and the modified crystalline microporous PST-16 consists of athree-dimensional framework of [M²⁺O_(4/2)]², [EO_(4/2)] and [PO_(4/2)]⁺tetrahedral units derived from crystalline microporous PST-16 via themodification processes of calcination, ammonia calcinations,ion-exchange, steaming, various acid extractions, ammoniumhexafluorosilicate treatment, or any combination thereof.
 18. Theprocess of claim 17 wherein the hydrocarbon conversion process isselected from the group consisting of cracking, hydrocracking,alkylation, isomerization, polymerization, reforming, hydrogenation,dehydrogenation, transalkylation, dealkylation, hydration, dehydration,hydrotreating, hydrofining, hydrodenitrogenation, hydrodesulfurization,methanol to olefins, methanation, syngas shift process, olefindimerization, oligomerization, dewaxing, and combinations thereof.